Hydrolysis resistant organomodified disiloxane surfactants

ABSTRACT

Disiloxane compounds of the formula 
 
MM′
Where M comprises either branched allyl hydrocarbon substituents or silanyl substituents and M comprises an alkylpolyalkyleneoxide substituent The disiloxane compounds of the invention exhibit an enhanced resistance to hydrolysis outside a pH range ranging from 6 to 7.5, and are useful as surfactants.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Ser.No. 60/726,409, filed Oct. 13, 2005.

FIELD OF INVENTION

The present invention relates to disiloxane surfactant compositions thatexhibit resistance to hydrolysis over a wide pH range. More particularlythe present invention relates to such hydrolysis resistant disiloxanesurfactants having a resistance to hydrolysis between a pH of about 3 toa pH of about 12.

BACKGROUND OF THE INVENTION

The topical application of liquid compositions to the surfaces of bothanimate and inanimate objects to effect a desired change involve theprocesses of controlling wetting, spreading, foaming, detergency, andthe like. When used in aqueous solutions to improve the delivery ofactive ingredients to the surface being treated, trisiloxane typecompounds have been found to be useful in enabling the control of theseprocesses to achieve the desired effect. However, the trisiloxanecompounds may only be used in a narrow pH range, ranging from a slightlyacidic pH of 6 to a very mildly basic pH of 7.5. Outside this narrow pHrange, the trisiloxane compounds are not stable to hydrolysis undergoinga rapid decomposition.

SUMMARY OF THE INVENTION

The present invention provides for a silicone composition comprising asilicone having the formula:MM′where

-   -   M=R¹R²R³SiO_(1/2);    -   M′=R⁴R⁵R⁶SiO_(1/2);        with R¹ selected from the group consisting of branched        monovalent hydrocarbon radical of from 3 to 6 carbon atoms and        R⁷, where R⁷ is selected from the group consisting of        R⁸R⁹R¹⁰SiR¹² and (R⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_(1/2))        with R⁸, R⁹, and R¹⁰ each independently selected from the group        of monovalent hydrocarbon radicals having from 1 to 6 carbon        atoms and monovalent aryl or alkaryl hydrocarbon radicals having        from 6 to 13 carbon atoms and R¹² is a divalent hydrocarbon        radical having from 1 to 3 carbon atoms,

R² and R³ are each independently selected from the group of from 1 to 6carbon atom monovalent hydrocarbon radicals or R¹, with R⁴ analkylpolyalkyleneoxide of the general formula:R¹³(C₂H₄O)_(a)(C₃H₆O)_(b)(CH₈O)_(c)R¹⁴where R¹³ is a divalent linear or branched hydrocarbon radical havingthe structure:—CH₂—CH(R¹⁵)(R¹⁶)_(d)O—where R¹⁵ is H or methyl; R¹⁶ is a divalent alkyl radical of 1 to 6carbons where the subscript d may be 0 or 1;

R¹⁴ is selected from the group consisting of H, monovalent hydrocarbonradicals of from 1 to 6 carbon atoms and acetyl where the subscripts a,b and c are zero or positive and satisfy the following relationships:2≦a+b+c≦20with a≦2,and R⁵ and R⁶ are each independently selected from the group ofmonovalent hydrocarbon radicals having from 1 to 6 carbon atoms or R⁴.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, integer values of stoichiometric subscripts refer tomolecular species and non-integer values of stoichiometric subscriptsrefer to a mixture of molecular species on a molecular weight averagebasis, a number average basis or a mole fraction basis.

The present invention provides for a disiloxane compound or compositionsthereof useful as a surfactant having the general formula:MM′where

-   -   M=R¹R²R³SiO_(1/2;)    -   M′=R⁴R⁵R⁶SiO_(1/2;)        with R¹ a branched monovalent hydrocarbon radical of from 3 to 6        carbon atoms or R⁷, where R⁷ is selected from the group        consisting of        R⁸R⁹R¹⁰SiR¹² and (R⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_(1/2))        with R⁸, R⁹, and R¹⁰ each independently selected from the group        of monovalent hydrocarbon radicals having from 1 to 6 carbon        atoms and monovalent aryl or alkaryl hydrocarbon radicals having        from 6 to 13 carbon atoms and R¹² is a divalent hydrocarbon        radical having from 1 to 3 carbon atoms,

R² and R³ are each independently selected from the group of from 1 to 6carbon atom monovalent hydrocarbon radicals or R¹, with R⁴ analkylpolyalkyleneoxide of the general formula:R¹³(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)R¹⁴where R¹³ is a divalent linear or branched hydrocarbon radical havingthe structure:—CH₂—CH(R¹⁵)(R¹⁶)_(d)O—where R¹⁵ is H or methyl; R¹⁶ is a divalent alkyl radical of 1 to 6carbons where the subscript d may be 0 or 1;

R¹⁴ is selected from the group consisting of H, monovalent hydrocarbonradicals of from 1 to 6 carbon atoms and acetyl subject to thelimitation that the subscripts a, b and c are zero or positive andsatisfy the following relationships:2≦a+b+c≦20with a≦2,and R⁵ and R⁶ are each independently selected from the group ofmonovalent hydrocarbon radicals having from 1 to 6 carbon atoms or R⁴.When the subscript a satisfies the condition 2≦a≦4 it is advisable toutilize a co-surfactant as hereinafter set forth in order to obtain thebenefit of the compositions of the present invention.

One method of producing the composition of the present invention is toreact a molecule of the following formula:MM^(H)where M^(H) is the hydride precursor to the M′ structural unit in thecomposition of the present invention, wherein the definitions andrelationships are later defined and consistent with those defined above,under hydrosilylation conditions, with an olefinically modifiedpolyalkyleneoxide, such as allyloxypolyethyleneglycol, ormethallyloxypolyalkyleneoxide, which are incorporated herein asexamples, and not set forth to limit other possible olefinicallymodified alkyleneoxide components. As used herein the phrase“olefinically modified polyalkyleneoxide” is defined as a moleculepossessing one or more alkyleneoxide groups containing one or more,terminal or pendant, carbon-carbon double bonds. The polyether is anolefinically modified polyalkyleneoxide (hereinafter referred to as“polyether”) is described by the general formula:CH₂═CH(R²⁵)(R¹⁶)_(d)O(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)R¹⁴where

R¹⁵ is H or methyl; R¹⁶ is a divalent alkyl radical of 1 to 6 carbonswhere the subscript d may be 0 or 1; R¹⁴ is H, a monofunctionalhydrocarbon radical of 1 to 6 carbons, or acetyl. When the polyether iscomposed of mixed oxyalkyleneoxide groups (i.e. oxyethylene,oxypropylene and oxybutylene) the units may be blocked, or randomlydistributed. One skilled in the art will understand the advantages ofusing a blocked or random configuration. Illustrative examples ofblocked configurations are: -(oxyethylene)_(a)(oxypropylene)_(b)-;-(oxybutylene)_(c)(oxyethylene)_(a)-; and-(oxypropylene)_(b)(oxyethylene)_(a)(oxybutylene)_(c)-

Illustrative examples of the polyether are provided below, but notlimited to:CH₂═CHCH₂O(CH₂CH₂O)₈H;CH₂═CHCH₂O(CH₂CH₂O)₈CH_(3;)CH₂═CHCH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅H;CH₂═CHO(CH₂CH₂O)₅(CH₂CH(CH₃)O)₅H;CH₂═C(CH₃)_(c)H₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅C(═O)_(c)H₃;CH₂═CHCH₂O(CH₂CH₂O)₅(CH₂CH(CH₃)O)₂(CH₂CH(CH₂CH₃)O)₂H

Polyether modified siloxanes are prepared in the normal manner throughthe use of a hydrosilylation reaction to graft the olefinically modified(i.e. vinyl, allyl or methallyl) polyalkyleneoxide onto the hydride(SiH) intermediate of the disiloxane of the present invention.

Precious metal catalysts suitable for making polyether-substitutedsiloxanes are also well known in the art and comprise complexes ofrhodium, ruthenium, palladium, osmium, iridium, and /or platinum. Manytypes of platinum catalysts for this SiH olefin addition reaction areknown and such platinum catalysts may be used to generate thecompositions of the present invention. The platinum compound can beselected from those having the formula (PtCl₂Olefin) and H(PtCl₃Olefin)as described in U.S. Pat. No. 3,159,601, hereby incorporated byreference. A further platinum containing material can be a complex ofchloroplatinic acid with up to 2 moles per gram of platinum of a memberselected from the class consisting of alcohols, ethers, aldehydes andmixtures thereof as described in U.S. Pat. No. 3,220,972 herebyincorporated by reference. Yet another group of platinum containingmaterials useful in this present invention is described in U.S. Pat.Nos. 3,715,334; 3,775,452 and 3,814,730 (Karstedt). Additionalbackground concerning the art may be found in J. L. Spier, “HomogeneousCatalysis of Hydrosilatidn by Transition Metals”, in Advances inOrganometanic Chemistry, volume 17, pages 407 through 447, F. G. A.Stone and R. West editors, published by Academic Press (New York, 1979).Those skilled in the art can easily determine an effective amount ofplatinum catalyst. Generally an effective amount ranges from about 0.1to 50 parts per million of the total organomodified disiloxanecomposition.

The compositions of the present invention exhibit an enhanced resistanceto hydrolysis outside a pH range ranging from 6 to 7.5. Enhancedresistance to hydrolysis can be demonstrated by a variety of tests butas used herein enhanced resistance to hydrolysis means 50 mole percentor more of the hydrolysis resistant composition of the present inventionremains unchanged or unreacted after a period of a twenty-four exposureto aqueous acidic conditions where the solution has a pH lower than 6 orafter a period of a twenty-four hour exposure to aqueous basicconditions where the solution has a pH greater than 7.5. Under acidicconditions the compositions of the present invention show a survival of50 mole percent of the original concentration or greater at a pH of 5 orless for a period of time in excess of 48 hours; specifically thecompositions of the present invention show a survival of 50 mole percentor greater at a pH of 5 or less for a period of time in excess of 2weeks; more specifically the compositions of the present invention showa survival of 50 mole percent or greater at a pH of 5 or less for aperiod of time in excess of 1 month; and most specifically thecompositions of the present invention show a survival of 50 mole percentor greater at a pH of 5 or less for a period of time in excess of 6months. Under basic conditions the compositions of the present inventionshow a survival of 50 mole percent or greater at a pH of 8 or more for aperiod of time in excess of 2 weeks; specifically the compositions ofthe present invention show a survival of 50 mole percent or greater at apH of 8 or more for a period of time in excess of 4 weeks; morespecifically the compositions of the present invention show a survivalof 50 mole percent or greater at a pH of 8 or more for a period of timein excess of 6 months; and most specifically the compositions of thepresent invention show a survival of 50 mole percent or greater at a pHof 8 or more for a period of time in excess of 1 year.

Uses for the Compositions of the Present Invention

A. Pesticide—Agriculture, Horticulture, Turf, Ornamental and Forestry:

Many pesticide applications require the addition of an adjuvant to thespray mixture to provide wetting and spreading on foliar surfaces. Oftenthat adjuvant is a surfactant, which can perform a variety of functions,such as increasing spray droplet retention on difficult to wet leafsurfaces, enhance spreading to improve spray coverage, or to providepenetration of the herbicide into the plant cuticle. These adjuvants areprovided either as a tank-side additive or used as a component inpesticide formulations.

Typical uses for pesticides include agricultural, horticultural, turf,ornamental, home and garden, veterinary and forestry applications.

The pesticidal compositions of the present invention also include atleast one pesticide, where the organomodified disiloxane surfactant ofthe present invention is present at an amount sufficient to deliverbetween 0.005% and 2% to the final use concentration, either as aconcentrate or diluted in a tank mix. Optionally the pesticidalcomposition may include excipients, cosurfactants, solvents, foamcontrol agents, deposition aids, drift retardants, biologicals,micronutrients, fertilizers and the like. The term pesticide means anycompound used to destroy pests, e.g., rodenticides, insecticides,miticides, fungicides, and herbicides. Illustrative examples ofpesticides that can be employed include, but are not limited to, growthregulators, photosynthesis inhibitors, pigment inhibitors, mitoticdisrupters, lipid biosynthesis inhibitors, cell wall inhibitors, andcell membrane disrupters. The amount of pesticide employed incompositions of the invention varies with the type of pesticideemployed. More specific examples of pesticide compounds that can be usedwith the compositions of the invention are, but not limited to,herbicides and growth regulators, such as: phenoxy acetic acids, phenoxypropionic acids, phenoxy butyric acids, benzoic acids, triazines ands-triazines, substituted ureas, uracils, bentazon, desmedipham,methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone,norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin,prodiamnine, trifluralin, glyphosate, sulfonylureas, imidazolinones,clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl,haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, andbipyridylium compounds.

Fungicide compositions that can be used with the present inventioninclude, but are not limited to, aldimorph, tridemorph, dodemorph,dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole,furconazole, propiconazole, tebuconazole and the like; imazalil,thiophanate, benomyl carbendazim, chlorothialonil, dicloran,trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil,prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin,dodine, and metalaxyl.

Insecticide, larvacide, miticide and ovacide compounds that can be usedwith the composition of the present invention, but not limited to,Bacillus thuringiensis, spinosad, abamectin, doramectin, lepimectin,pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boricacid, chlordimeform, novaluron, bistrifluron, triflumuron,diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan,dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos,clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrinand the like.

Fertilizers and Micronutrients:

Fertilizers and micronutrients include, but not limited to, zincsulfate, ferrous sulfate, ammonium sulfate, urea, urea ammoniumnitrogen, ammonium thiosulfate, potassium sulfate, monoammoniumphosphate, urea phosphate, calcium nitrate, boric acid, potassium andsodium salts of boric acid, phosphoric acid, magnesium hydroxide,manganese carbonate, calcium polysulfide, copper sulfate, manganesesulfate, iron sulfate, calcium sulfate, sodium molybdate, calciumchloride,

The pesticide or fertilizer may be a liquid or a solid. If a solid, itis preferable that it is soluble in a solvent, or the organomodifieddisiloxanes of the present invention, prior to application, and thesilicone may act as a solvent, or surfactant for such solubility oradditional surfactants may perform this function.

Agricultural Excipients:

Buffers, preservatives and other standard excipients known in the artalso may be included in the composition.

Solvents may also be included in compositions of the present invention.These solvents are in a liquid state at room temperature. Examplesinclude water, alcohols, aromatic solvents, oils (i.e. mineral oil,vegetable oil, silicone oil, and so forth), lower alkyl esters ofvegetable oils, fatty acids, ketones, glycols, polyethylene glycols,diols, paraffinics, and so forth. Particular solvents would be 2, 2,4-trimethyl, 1-3-pentane diol and alkoxylated (especially ethoxylated)versions thereof as illustrated in U.S. Pat. No. 5,674,832 hereinincorporated by reference, or n-methyl-pyrilidone.

Cosurfactants:

Cosurfactants useful herein include nonionic, cationic, anionic,amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof.Surfactants are typically hydrocarbon based, silicone based orfluorocarbon based.

Moreover, other cosurfactants, that have short chain hydrophobes that donot interfere with superspreading as described in U.S. Pat. No.5,558,806 herein incorporated by reference are also useful.

Useful surfactants include alkoxylates, especially ethoxylates,containing block copolymers including copolymers of ethylene oxide,propylene oxide, butylene oxide, and mixtures thereof;alkylarylalkoxylates, especially ethoxylates or propoxylates and theirderivatives including alkyl phenol ethoxylate; arylarylalkoxylates,especially ethoxylates or propoxylates. and their derivatives; aminealkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fattyalcohol alkoxylates; alkyl sulfonates; alkyl benzene and alkylnaphthalene sulfonates; sulfated fatty alcohols, amines or acid amides;acid esters of sodium isethionate; esters of sodium sulfosuccinate;sulfated or sulfonated fatty acid esters; petroleum sulfonates; N-acylsarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and soforth.

Specific examples include alkyl acetylenic diols (SURFONYL-AirProducts), pyrrilodone based surfactants (e.g., SURFADONE—LP 100—ISP),2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates (e.g., RHODASURF DA530—Rhodia), ethylene diamine alkoxylates (TETRONICS—BASF), ethyleneoxide/propylene oxide copolymers (PLURONICS—BASF), Gemini typesurfactants (Rhodia) and diphenyl ether Gemini type surfactants (e.g.DOWFAX—Dow Chemical).

Preferred surfactants include ethylene oxide/propylene oxide copolymers(EO/PO); amine ethoxylates; alkyl polyglycosides; oxo-tridecyl alcoholethoxylates, and so forth.

In a preferred embodiment, the agrochemical composition of the presentinvention further comprises one or more agrochemical ingredients.Suitable agrochemical ingredients include, but not limited to,herbicides, insecticides, growth regulators, fungicides, miticides,acaricides, fertilizers, biologicals, plant nutritionals,micronutrients, biocides, paraffinic mineral oil, methylated seed oils(i.e. methylsoyate or methylcanolate), vegetable oils (such as soybeanoil and canola oil), water conditioning agents such as Choices (LovelandIndustries, Greeley, CO) and Quest (Helena Chemical, Collierville, TN),modified clays such as Surround® (Englehard Corp.,), foam controlagents, surfactants, wetting agents, dispersants, emulsifiers,deposition aids, antidrift components, and water.

Suitable agrochemical compositions are made by combining, in a mannerknown in the art, such as, by mixing one or more of the above componentswith the organomodified disiloxane of the present invention, either as atank-mix, or as an “In-can” formulation. The term “tank-mix” means theaddition of at least one agrochemical to a spray medium, such as wateror oil, at the point of use. The term “In-can” refers to a formulationor concentrate containing at least one agrochemical component. The“In-can” formulation may then diluted to use concentration at the pointof use, typically in a Tank-mix, or it may be used undiluted.

Coatings:

Typically coatings formulations will require a wetting agent orsurfactant for the purpose of emulsification, compatibilization ofcomponents, leveling, flow and reduction of surface defects.Additionally, these additives may provide improvements in the cured ordry film, such as improved abrasion resistance, antiblocking,hydrophilic, and hydrophobic properties. Coatings formulations mayexists as, Solvent-borne coatings, water-borne coatings and powdercoatings.

The coatings components may be employed as: architecture coatings; OEMproduct coatings such as automotive coatings and coil coatings; SpecialPurpose coatings such as industrial maintenance coatings and marinecoatings;

Typical resin types include: Polyesters, alkyds, acrylics, epoxies

Personal Care

In a preferred embodiment, the organomodified disiloxane surfactant ofthe present invention comprises, per 100 parts by weight (“pbw”) of thepersonal care composition, from 0.1 to 99 pbw, more preferably from 0.5pbw to 30 pbw and still more preferably from 1 to 15 pbw of theorganomodified disiloxane surfactant and from 1 pbw to 99.9 pbw, morepreferably from 70 pbw to 99.5 pbw, and still more preferably from 85pbw to 99 pbw of the personal care composition.

The organomodified disiloxane surfactant compositions of the presentinvention may be utilized in personal care emulsions, such as lotions,and creams. As is generally known, emulsions comprise at least twoimmiscible phases one of which is continuous and the other which isdiscontinuous. Further emulsions may be liquids with varying viscositiesor solids. Additionally the particle size of the emulsions may renderthem microemulsions and, when sufficiently small, microemulsions may betransparent. Further it is also possible to prepare emulsions ofemulsions and these are generally known as multiple emulsions. Theseemulsions may be:

1) aqueous emulsions where the discontinuous phase comprises water andthe continuous phase comprises the organomodified disiloxane surfactantof the present invention;

2) aqueous emulsions where the discontinuous phase comprises theorganomodified disiloxane surfactant of the present invention and thecontinuous phase comprises water;

3) non-aqueous emulsions where the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises theorganomodified disiloxane surfactant of the present invention; and

4) non-aqueous emulsions where the continuous phase comprises anon-aqueous hydroxylic organic solvent and the discontinuous phasecomprises the organomodified disiloxane surfactant of the presentinvention.

Non-aqueous emulsions comprising a silicone phase are described in U.S.Pat. No. 6,060,546 and U.S. Pat. No. 6,271,295 the disclosures of whichare herewith and hereby specifically incorporated by reference.

As used herein the term “non-aqueous hydroxylic organic compound” meanshydroxyl containing organic compounds exemplified by alcohols, glycols,polyhydric alcohols and polymeric glycols and mixtures thereof that areliquid at room temperature, e.g. about 25° C., and about one atmospherepressure. The non-aqueous organic hydroxylic solvents are selected fromthe group consisting of hydroxyl containing organic compounds comprisingalcohols, glycols, polyhydric alcohols and polymeric glycols andmixtures thereof that are liquid at room temperature, e.g. about 25° C.,and about one atmosphere pressure. Preferably the non-aqueous hydroxylicorganic solvent is selected from the group consisting of ethyleneglycol, ethanol, propyl alcohol, iso-propyl alcohol, propylene glycol,dipropylene glycol, tripropylene glycol, butylene glycol, iso-butyleneglycol, methyl propane diol, glycerin, sorbitol, polyethylene glycol,polypropylene glycol mono alkyl ethers, polyoxyalkylene copolymers andmixtures thereof.

Once the desired form is attained whether as a silicone only phase, ananhydrous mixture comprising the silicone phase, a hydrous mixturecomprising the silicone phase, a water-in-oil emulsion, an oil-in-wateremulsion, or either of the two non-aqueous emulsions or variationsthereon, the resulting material is usually a cream or lotion withimproved deposition properties and good feel characteristics. It iscapable of being blended into formulations for hair care, skin care,antiperspirants, sunscreens, cosmetics, color cosmetics, insectrepellants, vitamin and hormone carriers, fragrance carriers and thelike.

The personal care applications where the organomodified disiloxanesurfactant of the present invention and the silicone compositionsderived therefrom of the present invention may be employed include, butare not limited to, deodorants, antiperspirants,antiperspirant/deodorants, shaving products, skin lotions, moisturizers,toners, bath products, cleansing products, hair care products such asshampoos, conditioners, mousses, styling gels, hair sprays, hair dyes,hair color products, hair bleaches, waving products, hair straighteners,manicure products such as nail polish, nail polish remover, nails creamsand lotions, cuticle softeners, protective creams such as sunscreen,insect repellent and anti-aging products, color cosmetics such aslipsticks, foundations, face powders, eye liners, eye shadows, blushes,makeup, mascaras and other personal care formulations where siliconecomponents have been conventionally added, as well as drug deliverysystems for topical application of medicinal compositions that are to beapplied to the skin.

In a preferred embodiment, the personal care composition of the presentinvention further comprises one or more personal care ingredients.Suitable personal care ingredients include, for example, emollients,moisturizers, humectants, pigments, including pearlescent pigments suchas, for example, bismuth oxychloride and titanium dioxide coated mica,colorants, fragrances, biocides, preservatives, antioxidants,anti-microbial agents, anti-fungal agents, antiperspirant agents,exfoliants, hormones, enzymes, medicinal compounds, vitamins, salts,electrolytes, alcohols, polyols, absorbing agents for ultravioletradiation, botanical extracts, surfactants, silicone oils, organic oils,waxes, film formers, thickening agents such as, for example, fumedsilica or hydrated silica, particulate fillers, such as for example,talc, kaolin, starch, modified starch, mica, nylon, clays, such as, forexample, bentonite and organo-modified clays.

Suitable personal care compositions are made by combining, in a mannerknown in the art, such as, for example, by mixing, one or more of theabove components with the organomodified disiloxane surfactant. Suitablepersonal care compositions may be in the form of a single phase or inthe form of an emulsion, including oil-in-water, water-in-oil andanhydrous emulsions where the silicone phase may be either thediscontinuous phase or the continuous phase, as well as multipleemulsions, such as, for example, oil-in water-in-oil emulsions andwater-in-oil-in water-emulsions.

In one useful embodiment, an antiperspirant composition comprises theorganomodified disiloxane surfactant of the present invention and one ormore active antiperspirant agents. Suitable antiperspirant agentsinclude, for-example, the Category I active antiperspirant ingredientslisted in the U.S. Food and Drug Administration's Oct. 10, 1993Monograph on antiperspirant drug products for over-the-counter humanuse, such as, for example, aluminum halides, aluminum hydroxyhalides,for example, aluminum chlorohydrate, and complexes or mixtures thereofwith zirconyl oxyhalides and zirconyl hydroxyhalides, such as forexample, aluminum-zirconium chlorohydrate, aluminum zirconium glycinecomplexes, such as, for example, aluminum zirconium tetrachlorohydrexgly.

In another useful embodiment, a skin care composition comprises theorganomodified disiloxane surfactant, and a vehicle, such as, forexample, a silicone oil or an organic oil. The skin care compositionmay, optionally, further include emollients, such as, for example,triglyceride esters, wax esters, alkyl or alkenyl esters of fatty acidsor polyhydric alcohol esters and one or more the known componentsconventionally used in skin care compositions, such as, for example,pigments, vitamins, such as, for example, Vitamin A, Vitamin C andVitamin E, sunscreen or sunblock compounds, such as, for example,titanium dioxide, zinc oxide, oxybenzone, octylmethoxy cinnamate,butylmethoxy dibenzoylm ethane, p-aminobenzoic acid and octyldimethyl-p-aminobenzoic acid.

In another useful embodiment, a color cosmetic composition, such as, forexample, a lipstick, a makeup or a mascara composition comprises theorganomodified disiloxane surfactant, and a coloring agent, such as apigment, a water soluble dye or a liposoluble dye.

In another useful embodiment, the compositions of the present inventionare utilized in conjunction with fragrant materials. These fragrantmaterials may be fragrant compounds, encapsulated fragrant compounds, orfragrance releasing compounds that either the neat compounds or areencapsulated. Particularly compatible with the compositions of thepresent invention are the fragrance releasing silicon containingcompounds as disclosed in U.S. Pat. Nos. 6,046,156; 6,054,547;6,075,111; 6,077,923; 6,083,901; and 6,153,578; all of which are hereinand herewith specifically incorporated by reference.

The uses of the compositions of the present invention are not restrictedto personal care compositions, other products such as waxes, polishesand textiles treated with the compositions of the present invention arealso contemplated.

D. Home Care

Home care applications include laundry detergent and fabric softener,dishwashing liquids, wood and furniture polish, floor polish, tub andtile cleaners, toilet bowl cleaners, hard surface cleaners, windowcleaners, antifog agents, drain cleaners, auto-dish washing detergentsand sheeting agents, carpet cleaners, prewash spotters, rust cleanersand scale removers.

EXPERIMENTAL

The hydride intermediates for the organomodified disiloxane surfactantcompositions of the present invention, as well as comparativecompositions were prepared as described in the following examples.

Preparation Example 1

1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (Structure 1). A250 mL round bottom flask was charged with tetramethyldisiloxane (51.6g) and Wilkinson's catalyst ((PPH₃)₃RhCl, 100 ppm), stirred under N₂,and brought to 60° C. Trimethylvinylsilane (25.6 g) was charged to anaddition funnel, added dropwise at a rate to maintain the reactiontemperature <70° C. with cooling (˜1 g/min). The reaction was maintained1 h @ 65° C., then sampled for GC; found residual tetramethyldisiloxaneand 94:6 M′M^(R): M^(R)M^(R)). Resulting material distilled fractionallyunder vacuum (approx. 30 mm Hg) to yield 51.6 g M′M^(R) product, 99.1%GC purity. This product was found to have an Si—H content of 96 cc H₂/gby gasiometric titration.

Preparation Example 2

1-(3,3-dimethylbutyl)-1,1,3,3-tetramethyldisiloxane (Structure 2). A 250mL round bottom flask was charged with tetramethyldisiloxane (46.1 g),and stirred under N₂. A solution of Karstedt's catalyst (Pt(O) indivinyltetamethyldisiloxane, 10 ppm) in 3,3-dimethyl-1-butene (19.3 g)was charged to an addition funnel, and added dropwise at a rate tomaintain the reaction temperature <40° C. with cooling (˜0.5 g/min). Thereaction was maintained 1 h @ 50° C., then sampled for GC; foundresidual tetramethyldisiloxane, M′M^(R) product, and M^(R)M^(R)byproduct (32:53:9). Resulting material distilled fractionally undervacuum (approx. 30 mm Hg) using a 25-cm Vigreux column to yield 25.0 gM′M^(R) product, >98.1% GC purity. This product was found to have anSi—H content of 100 cc H₂/g by gasiometric titration.

Preparation Example 3

1-(2-methylpropyl)-1,1,3,3-tetramethyldisiloxane (Structure 3). An 80 mLFischer-Porter high pressure bottle was charged withtetramethyldisiloxane (10.0 g), toluene (10.0 g) and Wilkinson'scatalyst ((PPH₃)₃RhCl, 40 ppm), stirred and brought to 60° C. The bottlewas attached to a manifold and pressurized with isobutylene (25 psig)and maintained at 60-70° C. for 8 h. The pressure was vented, and thereaction was sampled for GC analysis; found residualtetramethyldisiloxane, M′M^(R) product and M^(R)M^(R) byproduct(2:95:3). The resulting material was stripped under vacuum (approx. 150mm Hg) at 40° C. to remove olefin and M′M′, then filtered with Celite toyield 21.3 g M′M^(R) product/toluene solution, 94% GC purity. Thisproduct was found to have an Si—H content of 11 cc H₂/g by gasiometrictitration.

Preparation Example 4

1-propyl-1,1,3,3-tetramethyldisiloxane (Structure 4). An 80 mLFischer-Porter high pressure bottle was charged withtetramethyldisiloxane (10.0 g), toluene (10.0 g) and Wilkinson'scatalyst ((PPH₃)₃RhCl, 40 ppm), stirred and brought to 50° C. The bottlewas attached to a manifold and pressurized with propylene (40 psig) andmaintained at 50° C. for 2 h. The pressure was vented, and the reactionwas sampled for GC analysis; found M′M^(R) product and M^(R)M^(R)byproduct (40:60). The resulting mixture of materials was used withoutfurther purification, yield 14.1 g.

Preparation Example 5

1-tert-butyl-1,1,3,3-tetramethyldisiloxane (Structure 5). A 1L roundbottom flask was charged with water (95 g) and diisopropyl ether (50 g)and stirred. A solution of tert-butyldimethylsilyl chloride (39.5 g) inisopropyl ether (50 g) was charged to an addition funnel, and addeddropwise to the water/IPE mixture at a rate to maintain the reactiontemperature between 30-35° C. After complete addition, the reactiontemperature was brought to 40° C. and maintained for 1 h. A solution ofdimethylchlorosilane (24.8 g) in isopropyl ether (50 g) was then chargedto the addition funnel, and this solution was added dropwise at 40-45°C. After complete addition, the reaction mixture was heated to refluxfor 1 h and allowed to cool. After aqueous workup (washing with waterand aqueous NaHCO₃, and drying organic fractions over MgSO₄), theproduct was isolated by fractional distillation under vacuum to yield39.2 g M(R)M′ product/isopropyl ether solution (70%/20% by GC analysis).This product was found to have an Si—H content of 79 cc H₂/g bygasiometric titration.

Preparation Example 6

1-(dicyclopentadienyl)-1,1,3,3-tetramethyldisiloxane (Structure 6). A250 mL RBF was charged with tetramethyldisiloxane (45.3 g), stirredunder N₂, and brought to 40° C. A solution of Karstedt's catalyst (Pt(O)in divinyltetamethyldisiloxane, 40 ppm) in dicyclolpentadiene (29.8 g)was charged to an addition funnel, and added dropwise at a rate tomaintain the reaction temperature <60° C. with cooling (˜0.5 g/min).After complete addition, the reaction was maintained 1 h @ 60° C. Thereaction mixture was stripped in vacuo (˜30 mm Hg) at 100° C. to yield41.1 g M′M^(R) product, >96% GC purity. This product was found to havean Si—H content of 81 cc H₂/g by gasiometric titration.

Preparation Example 7

The hydride intermediates of Examples 1-6 were further modified withvarious allylpolyalkyleneoxides to yield the organomodified disiloxanecompositions of this instant invention (From Examples 1,2, 3 and 5), aswell as the comparative disiloxane surfactants (From Examples 4 and 6).

Additionally comparative trisiloxane alkoxylates were preparedconventional methods of platinum mediated hydrosilation, as described inley, U.S. Pat. No. 3,299,112, herein incorporated by reference.

Table 1 provides a description of the compositions of the presentinvention. These compositions are described by the general structure:M*M″where M*=R¹Si(CH₃)₂O_(0.5); M″=O_(0.5)Si(CH₃)₂Qwhere R¹ is described in Table 2;Q=—CH₂CH₂CH₂O(CH₂CH₂O)_(a)(CH₂CH(CH₃)O)_(b)R² TABLE 1 Description ofOrganomodified Disioxane Surfactant Compositions I.D. R¹ a b R² 1(CH₃)₂CHCH₂— 7.5 0 CH₃ 2 CH₃CH₂CH₂— 7.5 0 CH₃ 3 (CH₃)₂CHCH₂— 7.5 0 H 4(CH₃)₂CHCH₂— 11 0 H 5 (CH₃)₃C— 7.5 0 CH₃ 6 (CH₃)₂CHCH₂— 7.5 0 H 7(CH₃)₂CHCH₂— 11 0 H 8 (CH₃)₂CHCH₂— 7.5 0 CH₃ 9 (CH₃)₃SiCH₂CH₂— 7.5 0 H10 (CH₃)₃SiCH₂CH₂— 7.5 0 CH₃ 11 (CH₃)₃SiCH₂CH₂— 11 0 H 12(CH₃)₃SiCH₂CH₂— 5 2.5 H 13 (CH₃)₃SiCH₂CH₂— 6.3 0 H

Table 2 provides a description of the comparative disiloxane basedsurfactants. TABLE 2 Comparative Siloxane Based Surfactants I.D. R¹ a bR² A CH₃—  7.5 0 H B CH₃—  7.5 0 CH₃ C CH₃— 11 0 H D

11 0 H H

 7.5 0 HTable 3 provides a description of the comparative organosiliconepolyether based surfactants of the general structure:

where Z=−CH₂CH₂CH₂O(CH₂CH₂O),(CH₂CH(CH₃)O)_(b)R² TABLE 3 Composition ofComparative Organosilicone Polyether Surfactants Z Group I.D. x y a b R²E 0 1 7.5 0 CH₃ F 0 1 7.5 0 H G 20 3 7.5 0 CH₃

Additionally, comparative sample OPE (Octylphenolethoxylate, containing10 polyoxyethylene units) is a non-silicone organic surfactant. Thisproduct is available as Triton® X-100 from Dow Chemical Company,Midland, Mich.

Example 8

This example demonstrates the ability of the organomodified disiloxanecomposition of the present invention to reduce aqueous surface tensionthereby showing utility as surfactants. Surface tension was measuredusing a Kruss surface tensiometer, with a sand blasted platinum blade asthe sensor. Solutions of the various components were prepared at 0.1 wt% in 0.005M NaCl water (Deionized), as an equilibrium aid.

Table 4 shows that solutions of these unique compositions provide asignificant reduction in surface tension relative to the conventionalsurfactant.

The compositions of the present invention also provide spreadingproperties similar to the TSAs (E and F), and comparative disiloxanesurfactants (A, B, C, D and H). Additionally, organomodified disiloxanesurfactants of the present invention provide improved spreading relativeto the conventional silicone polyether (G) and conventional organicsurfactant product OPE (Table 4).

Spreading was determined by applying a 10 μL droplet, of surfactantsolution to polyacetate film (USI, “Crystal Clear Write on Film”) andmeasuring the spread diameter (mm) after 30 seconds, at a relativehumidity between 50 and 70% (at 22 to 25° C.). The solution was appliedwith an automatic pipette to provide droplets of reproducible volume.Deionized water that was further purified with a Millipore filtrationsystem was used to prepare the surfactant solutions. TABLE 4 SurfaceTension and Spreading Properties Surface Tension Spread Diameter (mm)I.D. mN/m 0.1% 0.2% 0.4% 1 23.3 40 42 50 2 23.6 34 36 33 3 24.0 12 14 244 24.1 8 9 10 5 23.5 32 48 45 6 23.2 41 33 23 7 23.9 14 15 25 8 24.0 2333 41 9 22.8 14 25 49 10 23.0 15 27 34 11 24.5 20 21 32 12 24.3 7 8 1013 22.2 14 32 27 A 23.4 8 36 58 B 24.3 8 12 44 C 24.1 6 8 9 D 32.7 7 ndnd E 20.9 53 51 25 F 20.6 53 50 35 G 23.6 nd nd 6 H nd nd nd 7 OPE 31.8nd nd 10

Example 9

Hydrolytic stability was determined for representative compositions ofthe present invention using HPLC. Solutions of the various compositionswere prepared at 0.5 wt % over a pH range from pH 4 to pH12, andmonitored by HPLC for decomposition as a function of time.

Analytical Method:

The samples were analyzed by a reverse-phase chromatographic techniqueusing the experimental conditions listed in Table 5. TABLE 5 SolventGradient for HPLC Method Time (min.) % Methanol % Water % Isopropanol0.0 70 30 0 15.0 100 0 0 20.0 50 0 50 20.1 70 30 0 25.0 70 30 0

-   Detector: ELSD/LTA (Evaporative Light Scattering with Low    Temperature Adapter-   Conditions: 30° C., 1.95 SLPM N₂-   Column: Phenomenex LUNA C18 end cap, 5 micron, 75×4.6 mm-   Flow Rate: 1.0 mL/min.-   Inj. Volume: 10 microlitres-   Sample: 0.050 g/mL in methanol

Tables 6-16 demonstrates that the compositions of the present inventionprovide improved resistance to hydrolytic decomposition relative to thestandard comparative siloxane-based surfactants siloxanes B and E undersimilar pH conditions.

Comparative siloxanes B and E show rapid hydrolysis at ≦pH₅ and >pH 7,while the organomodified disiloxane surfactants of the present inventiondemonstrate a higher resistance to hydrolysis under the same conditions.

Although comparative D shows similar resistance to hydrolysis, it doesnot provide the enhanced spreading properties associated with theorganomodified disiloxane surfactants of the present invention. Forexample comparative D gave a spread diameter of only 6 mm (0.4%) and had82% product remaining by HPLC, after 48 h at pH₄, while theorganomodified disiloxane surfactant product 10 gave a spread diameterof 34 mm and maintained 75% product after 1 week, under the sameconditions (Tables 4, 11 and 16). TABLE 6 Hydrolytic Stability ofSiloxane Based Surfactants by HPLC Stability: % Sioxane SurfactantRemaining I.D. Time pH 4 pH 5 pH 7 pH 9 pH 10 pH 11 pH 12 1  24 h 83 100100 100 100 100 nd   1 wk 8 71 100 100 100 68 nd 2.5 wk 1 38 100 100 8335 nd  15 wk 0.5 4 100 100 42 28 nd

TABLE 7 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Sioxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 2  24 h 23 88 100 100 100 79 nd   1 wk 1 26 100 95 6917 nd 2.5 wk 0 7 100 89 44 7 nd

TABLE 8 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Siloxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 5 1 wk 65 100 100 100 100 100 nd 4 wk 32 76 100 100100 100 nd 6 wk 21 64 100 100 100 100 nd

TABLE 9 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Siloxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 8 24 h 84 100 100 100 100 nd nd  1 wk 50 100 100 100100 nd nd  2 wk 31 79 100 100 100 nd nd  4 wk 21 65 100 97 88 nd nd 10wk 7 45 100 93 83 nd nd

TABLE 10 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Sioxane Surfactant Remaining I.D Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 9 24 h 92 100 100 100 100 nd nd  1 wk 67 100 100 100100 nd nd

TABLE 11 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Siloxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 10  24 h 100 100 100 100 100 100 79   1 wk 75 100 100100 100 93 42   2 wk 50 88 100 100 100 nd nd   3 wk 32 80 100 100 100 9334   7 wk nd nd nd nd nd 93 11 7.5 wk 12 56 100 100 100 nd nd  11 wk nd48 100 100 100 nd nd  13 wk nd nd nd nd nd 95 nd  17 wk nd nd 100 100 84nd nd  27 wk nd nd 100 100 86 100 nd

TABLE 12 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Siloxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 11 96 h 100 100 100 100 100 nd nd  3 wk 79 100 100 100100 nd nd  6 wk 56 100 100 100 100 nd nd 11 wk 10 100 100 100 100 nd ndNote:Stock Solution 2.5 wt %

TABLE 13 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Siloxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 13 24 h 100 100 100 100 100 nd nd  1 wk 56 100 100 100100 nd nd

TABLE 14 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Sioxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 E 48 h 25 100 100 100 46 nd nd  1 wk 0 38 100 53 0 ndnd

TABLE 15 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Siloxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 B 24 h 0 0 100 38 0 nd nd

TABLE 16 Hydrolytic Stability of Siloxane Based Surfactants by HPLCStability: % Slioxane Surfactant Remaining I.D. Time pH 4 pH 5 pH 7 pH 9pH 10 pH 11 pH 12 D 48 h 82 >95 >95 >95 >95 nd nd  9 days 44   99   99  99   99 nd nd

Examples 10-12

Unlike traditional siloxane based surfactants, which are subject torapid hydrolysis under acidic and basic conditions (≦pH 5 and ≦pH 9) theorganomodified disiloxane surfactants of the present invention provideincreased resistance to hydrolysis relative to traditional trisiloxanealkoxylates (Comparative E and F), as well as the comparativetrimethylsilyl terminated disiloxane surfactants, represented byComparative B. An artifact of hydrolysis is observed as a reduction insuperpsreading properties over time. Therefore solutions of theorganomodified disiloxane surfactants of the present invention, as wellas comparative surfactants were prepared at desired use levels and pH.Spreading was determined as a function of time to illustrate resistanceto hydrolysis.

Example 10

Table 17 is an illustrative example of the organomodified disiloxanesurfactants, where product No. 10, has improved resistance tohydrolysis, at pH 3, relative to a traditional trisiloxane ethoxylatesuperspreading surfactant (Product E). As mentioned above, resistance tohydrolysis was observed by monitoring the spreading properties overtime. Here a 0.4 wt % solution was prepared at pH 3, and spreadingdetermined according to the procedure in Example 8.

Example 11

In another example the organomodified disiloxane surfactants of thepresent invention represented by product Nos. 6 and 11, demonstrateimproved resistance to hydrolysis relative to product F, a trisiloxaneethoxylate superspreader (Table 18). Solutions (0.4 wt %) of thesurfactants were prepared at pH 4 and pH 5 and spreading properties wereobserved over time. The test conditions are outlined in Example 8. TABLE18 Spreading Properties at pH 4 and pH 5 Vs Time Spreading Diameter (mm)ID: 6 6 11 11 F F Time pH 4 pH 5 pH 4 pH 5 pH 4 pH 5  0 h 50 46 16 26 5049  1 h 48 44 23 23 50 50  4 h 59 48 23 — 46 47 24 h 49 51 44 24 52 5148 h 40 49 38 32 39 49 72 h 42 50 28 35 16 48  1 wk 13 43 8 29 12 52  2wk 11 49 8 33 7 53  3 wk 18 47 12 33 6 21  1 mo 17 49 10 42 6 15

EXAMPLE 12

In another example the organomodified disiloxane surfactants of thepresent invention, represented by product No. 5, shows improvedresistance to hydrolysis relative to comparative product E. Heresurfactant solutions (0,1 wt %) were prepared at pH 4, pH 5, pH 8, pH 9and pH 10, and the spreading properties over time were observed asdescribed in Example 8.

Table 19 demonstrates that the comparative silicone E shows a more rapidloss of spreading properties at pH 4, pH 5, pH 9 and pH 10, than productNo. 5. TABLE 19 Spreading Properties vs. Time Spread Diameter (mm) TimeProduct pH 4 pH 5 pH 8 pH 9 pH 10  0 h 5 53 52 52 51 51 E 56 54 56 54 54 1 h 5 52 50 51 50 51 E 55 53 53 56 54  2 h 5 54 52 50 49 50 E 51 53 5555 52  4 h 5 51 50 50 48 49 E 41 51 56 53 49  6 h 5 51 50 50 48 49 E 3552 50 53 46  8 h 5 48 51 52 49 52 E 29 50 51 51 47  24 h 5 51 50 52 5149 E 7 50 53 50 32  48 h 5 39 48 46 46 41 E 6 41 47 43 10  72 h 5 33 4845 45 42 E 6 32 49 44 7  96 h 5 23 45 47 46 40 E 6 17 50 41 6 168 h 5 843 43 44 43 E 5 9 50 32 6

Example 13

The impact of other ingredients on spreading was determined by blendingthe organosilicone disiloxane surfactant of the present invention, witha conventional organic based cosurfactant. The cosurfactants aredescribed in Table 20.

Blends were prepared as physical mixtures where the weight fractionsilicone is represented by cc (alpha), indicating that the cosurfactantmakes up the balance of the blend ratio. For example when α=0 thisindicates that the composition contains 0% of the silicone component and100% cosurfactant, while an a=1.0 indicates the composition contains100% silicone, and no (0%) cosurfactant. Mixtures of the two componentsare represented by the weight fraction a, where a ranges as follows:0≦α≦1.0. By example when a =0.25 this indicates the surfactant mixtureis composed of 25% silicone and 75% cosurfactant. These blends are thendiluted in water to the desired concentration for spreading evaluation.

Spreading was determined as described in Example 8, at either 0.1 wt %or 0.2wt % total surfactant.

Table 21 demonstrates that representative examples of the cosurfactantsof the present invention provide favorable spreading results, and insome cases provide an unexpected synergistic enhancement, where thespread diameter of the mixture exceeds that of the individualcomponents. TABLE 20 Description of Conventional Cosurfactants IDDescription IDA-5 Isodecyl alcohol ethoxylate (4-5 EO) IDA-6 Isodecylalcohol ethoxylate (5-6 EO) TMN-6 Trimethylnonylalcohol ethoxylate (6EO) Oxo-TDA-5 Oxo-tridecyl alcohol ethoxylate (5 EO) Oxo-TDA-6Oxo-tridecyl alcohol ethoxylate (6 EO) APG C₈₋₁₀ Alkylpolyglucoside

TABLE 21 Effect of Cosurfactants on Blend Spreading Properties WtFraction (α) Silicone Surfactant Spread diameter (mm) Run Silicone 00.25 0.50 0.75 1.0 Cosurfactant 1 10^(a) 45 49 23 17 25 IDA-5 2 10^(a)35 38 47 26 25 IDA-6 3 10^(a) 41 38 42 36 25 TMN-6 4 10^(a) 34 29 23 1925 Oxo-TDA-5 5 10^(a) 39 42 49 36 25 Oxo-TDA-6 6 10^(a) 10 39 42 35 25APG 7  5^(b) 41 46 47 49 50 IDA-5 8  5^(b) 19 31 35 46 50 IDA-6 9  5^(b)34 38 44 45 50 TMN-6 10  5^(b) 36 40 44 51 50 Oxo-TDA-5 11  5^(b) 38 4039 46 50 Oxo-TDA-6 12  5^(b) 8 32 40 48 50 APG^(a)0.2 wt % total surfactant^(b)0.1 wt % total surfactant

The foregoing examples are merely illustrative of the invention, servingto illustrate only some of the features of the present invention. Theappended claims are intended to claim the invention as broadly as it hasbeen conceived and the examples herein presented are illustrative ofselected embodiments from a manifold of all possible embodiments.Accordingly it is Applicants' intention that the appended claims are notto be limited by the choice of examples utilized to illustrate featuresof the present invention. As used in the claims, the word “comprises”and its grammatical variants logically also subtend and include phrasesof varying and differing extent such as for example, but not limitedthereto, “consisting essentially of” and “consisting of.” Wherenecessary, ranges have been supplied; those ranges are inclusive of allsub-ranges there between. Such ranges may be viewed as a Markush groupor groups consisting of differing pairwise numerical limitations whichgroup or groups is or are fully defined by its lower and upper bounds,increasing in a regular fashion numerically from lower bounds to upperbounds. It is to be expected that variations in these ranges willsuggest themselves to a practitioner having ordinary skill in the artand where not already dedicated to the public, those variations shouldwhere possible be construed to be covered by the appended claims. It isalso anticipated that advances in science and technology will makeequivalents and substitutions possible that are not now contemplated byreason of the imprecision of language and these variations should alsobe construed where possible to be covered by the appended claims. AllUnited States patents (and patent applications) referenced herein areherewith and hereby specifically incorporated by reference in theirentirety as though set forth in full.

1. A silicone composition comprising a silicone having the formula:MM′ where M=R¹R²R³SiO_(1/2); M′=R⁴R⁵R⁶SiO_(1/2); with R¹ selected fromthe group consisting of branched monovalent hydrocarbon radical of from3 to 6 carbon atoms and R⁷, where R⁷ is selected from the groupconsisting ofR⁸R⁹R¹⁰SiR¹² and (R⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_(1/2)) with R⁸, R⁹, and R¹⁰each independently selected from the group of monovalent hydrocarbonradicals having from 1 to 6 carbon atoms and monovalent aryl or alkarylhydrocarbon radicals having from 6 to 13 carbon atoms and R¹² is adivalent hydrocarbon radical having from 1 to 3 carbon atoms, R² and R³are each independently selected from the group of from 1 to 6 carbonatom monovalent hydrocarbon radicals or R¹, with R⁴ analkylpolyalkyleneoxide of the general formula:R¹³(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)R¹⁴ where R¹³ is a divalent linearor branched hydrocarbon radical having the structure:—CH₂—CH(R¹⁵)(R¹⁶)_(d)O— where R¹⁵ is H or methyl; R¹⁶ is a divalentalkyl radical of 1 to 6 carbons where the subscript d may be 0 or 1; R¹⁴is selected from the group consisting of H, monovalent hydrocarbonradicals of from 1 to 6 carbon atoms and acetyl where the subscripts a,b and c are zero or positive and satisfy the following relationships:2≦a+b+c≦20 with a≧2, and R⁵ and R⁶ are each independently selected fromthe group of monovalent hydrocarbon radicals having from 1 to 6 carbonatoms or R⁴.
 2. The composition of claim 1 where R¹ is iso-propyl. 3.The composition of claim 1 where R¹ is iso-butyl.
 4. The composition ofclaim 1 where R¹ is tert-butyl.
 5. The composition of claim 1 where R¹is R⁷ where R⁷ has the formula: R⁸R⁹R¹⁰SiR¹² with R⁸, R⁹, and R¹⁰ eachmethyl and R¹² is a divalent hydrocarbon radical having 2 carbon atoms.6. The composition of claim 1 where R¹⁵ is hydrogen.
 7. The compositionof claim 1 where R² is methyl.
 8. The composition of claim 2 where R¹⁵is hydrogen.
 9. The composition of claim 2 where R² is methyl.
 10. Thecomposition of claim 3 where R¹⁵ is hydrogen.
 11. The composition ofclaim 3 where R² is methyl.
 12. The composition of claim 4 where R¹⁵ ishydrogen.
 13. The composition of claim 4 where R² is methyl.
 14. Thecomposition of claim 5 where R¹⁵ is hydrogen.
 15. The composition ofclaim 5 where R² is methyl.
 16. A silicone composition comprising asilicone having the formula:MM′ where M=R¹R²R³SiO_(1/2); M′=R⁴R⁵R⁶SiO_(1/2); with R¹ selected fromthe group consisting of branched monovalent hydrocarbon radical of from3 to 6 carbon atoms and R⁷, where R⁷ is selected from the groupconsisting ofR⁸R⁹R¹⁰SiR¹² and (R⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_(1/2)) with R⁸, R⁹, and R¹⁰each independently selected from the group of monovalent hydrocarbonradicals having from 1 to 6 carbon atoms and monovalent aryl or alkarylhydrocarbon radicals having from 6 to 13 carbon atoms and R¹² is adivalent hydrocarbon radical having from 1 to 3 carbon atoms, R² and R³are each independently selected from the group of from 1 to 6 carbonatom monovalent hydrocarbon radicals or R¹, with R⁴ analkylpolyalkyleneoxide of the general formula:R¹³(C₂H₄O)_(a)(C₃H₆O)_(b)(C₄H₈O)_(c)R¹⁴ where R¹³ is a divalent linearor branched hydrocarbon radical having the structure:—CH₂—CH(R¹⁵)(R¹⁶)_(d)O— where R¹⁵ is H or methyl; R¹⁶ is a divalentalkyl radical of 1 to 6 carbons where the subscript d may be 0 or 1; R¹⁴is selected from the group consisting of H, monovalent hydrocarbonradicals of from 1 to 6 carbon atoms and acetyl where the subscripts a,b and c are zero or positive and satisfy the following relationships:2≦a+b+c≦20 with a≧2, and R⁵ and R⁶ are each independently selected fromthe group of monovalent hydrocarbon radicals having from 1 to 6 carbonatoms or R⁴ wherein said silicone composition has an enhanced resistanceto hydrolysis.
 17. The composition of claim 16 where R¹ is iso-propyl.18. The composition of claim 16 where R¹ is iso-butyl.
 19. Thecomposition of claim 16 where R¹ is tert-butyl.
 20. The composition ofclaim 16 where R¹ is R⁷ where R⁷ has the formula: R⁸R⁹R¹⁰SiR¹² with R⁸,R⁹, and R¹⁰ each methyl and R¹² is a divalent hydrocarbon radical having2 carbon atoms.
 21. The composition of claim 16 where R¹⁵ is hydrogen.22. The composition of claim 16 where R² is methyl.
 23. The compositionof claim 17 where R¹⁵ is hydrogen.
 24. The composition of claim 17 whereR² is methyl.
 25. The composition of claim 18 where R¹⁵ is hydrogen. 26.The composition of claim 18 where R² is methyl.
 27. The composition ofclaim 19 where R¹⁵ is hydrogen.
 28. The composition of claim 19 where R²is methyl.
 29. The composition of claim 20 where R¹⁵ is hydrogen. 30.The composition of claim 20 where R² is methyl.
 31. An aqueous emulsionwherein the discontinuous phase comprises water and the continuous phasecomprises the composition of claim
 1. 32. An aqueous emulsion whereinthe discontinuous phase comprises water and the continuous phasecomprises the composition of claim
 16. 33. An aqueous emulsion whereinthe continuous phase comprises water and the discontinuous phasecomprises the composition of claim
 1. 34. An aqueous emulsion whereinthe continuous phase comprises water and the discontinuous phasecomprises the composition of claim
 16. 35. A non-aqueous emulsionwherein the discontinuous phase comprises a non-aqueous hydroxylicsolvent and the continuous phase comprises the composition of claim 1.36. A non-aqueous emulsion wherein the discontinuous phase comprises anon-aqueous hydroxylic solvent and the continuous phase comprises thecomposition of claim
 16. 37. A non-aqueous emulsion wherein thecontinuous phase comprises a non-aqueous hydroxylic solvent and thediscontinuous phase comprises the composition of claim
 1. 38. Anon-aqueous emulsion wherein the continuous phase comprises anon-aqueous hydroxylic solvent and the discontinuous phase comprises thecomposition of claim 16.